Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/409—Dispersions of polymers of C08G in organic compounds having active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/58—Epoxy resins
  • C08G18/584—Epoxy resins having nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
  • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0016—Foam properties semi-rigid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0025—Foam properties rigid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/005—< 50kg/m3
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S521/902—Cellular polymer containing an isocyanurate structure

Definitions

• the present invention relates to polyurethane foams.
• Polyurethane foams have been very well accepted for many years because of their well known advantages and because of the wide variety of applications for which the foams can be used.
• Flexible and semi-flexible foams are commonly used, among other things, for furniture cushioning, for the fabrication of matresses and in many transportation means, for example for cushioning of seats. For these applications, it is often desirable to use flexible or semi-flexible polyurethane foams with high resilient and/or high load bearing properties.
• modified polyol for preparing flexible polyurethane foams with high load bearing properties.
• the modified polyols are made by reacting an initiator having an active hydrogen functionality of from 3 to 4 with one or more alkylene oxides to extend the polyol chain, and adding epoxy resin in such a manner that it is inserted at selected points internally along the length of the polyol chain.
• the flexible foams have several disadvantages, e.g. the foams are not highly resilient and they are difficult to produce.
• one aspect of the present invention is a polyurethane foam which is the reaction product of at least one polyol and at least one polyisocyanate in the presence of at least one blowing agent characterized in that the polyol is at least partially a polymer polyol dispersion prepared by reacting an epoxy resin with an epoxy hardener in the presence of a liquid polyol.
• a further aspect of the present invention is a process for preparing a polyurethane foam by reacting at least one polyol and at least one polyisocyanate in the presence of at least one blowing agent, which process is characterized in that the above mentioned polymer polyol dispersion is employed.
• the physical properties of the polyurethane foam can be influenced selectively, depending on the type and amount of epoxy resin and epoxy hardener used.
• the epoxy resins and epoxy hardeners are dissolved in the polyols in such quantities that the resultant polymer polyol dispersions contain 1 to 50 percent by weight, preferably 5 to 30 percent by weight, polymer particles, based on the total weight of the dispersion. It is of little consequence whether the reagents are dissolved in the polyol together or whether one of the components is placed in the polyol and the other is added as necessary for the reaction. Following this, the polyaddition reaction is allowed to take place at a rate of reaction which can be adjusted by means of the reaction temperature. During this process, the initially clear solution changes into a milky dispersion.
• the size of the polymer particles in the polyol dispersion can be influenced by the selection of the raw materials as well as their concentration in the polyol and the reaction temperature. Reaction temperatures of generally 0° C to 150° C, preferably 20°C to 100°C, most preferably 20°C to 60°C, work well.
• reaction temperature is too high, agglomeration of the solid particles can take place, depending on the solids content of the dispersion. It is however within the knowledge of the skilled artisan to choose the appropriate reaction temperature.
• reaction times are a function of the temperature and are dependent upon the chemical structure of the epoxy resins and the epoxy hardeners.
• the rate of the polyaddition reaction can be influenced by the amine's basicity as well as by steric factors.
• the reaction times are between 30 minutes and 10 days, preferably between 12 hours and 72 hours.
• poly as used herein, for example in the terms polyepoxide, polyhydric, polyol and polyisocyanate, means two or more.
• Suitable examples include epoxy resins from the reaction of polyphenols and epihalohydrins, polyalcohols and epihalo- . hydrins, amines and epihalohydrins, sulfur-containing compounds and epihalohydrins, polycarboxylic acids and epihalohydrins, polyisocyanates and 2,3-epoxy-l-propanol (glycide) and from epoxidation of olefinically unsaturated compounds.
• Preferred epoxy resins are the reaction products of polyphenols and epihalohydrins, of polyalcohols and epihalohydrins or of polycarboxylic acids and epihalohydrins. Mixtures of polyphenols, polyalcohols, amines, sulfur-containing compounds, polycarboxylic acids and/or polyisocyanates can also be reacted with epihalohydrins.
• expoxy resins useful herein are described in The Handbook of Epoxy Resins by H.Lee and K.Neville, published in 1967 by McGraw-Hill, New York, in appendix 4-1, ppgs thru 4-56 and U.S. Patent Nos. 2,633,458; 3,477,990 (particularly column 2, line 39 to colum 4, line 75); 3,821,243; 3,970,719; 3,975,397 and 4,071,477 and G.B. Patent Specification No. 1,597,610, all of which are incorporated herein by reference.
• Epoxy resins of particular interest in the practice of the present invention include diglycidyl ethers of bisphenol compounds, particularly those compounds represented by the following general structural formula: wherein: (I)
• the average epoxy equivalent weight is from 149, preferably from about 170, up to about 3000, preferably up to about 950, most preferably up to about 450.
• the average epoxy equivalent weight is the average molecular weight of the resin divided by the number of epoxy groups per molecule.
• the molecular weight is a weighted average molecular weight.
• Particularly preferred epoxy resins are those wherein each A is methylene or isopropylidene, each X is independently hydrogen or bromine and n is on the average from 0 to 2.
• Preferred examples of these resins are bisphenol A type epoxy resins having an average epoxy equivalent weight of from about 170 to about 200. Such resins are commercially available from The Dow Chemical Company as D.E.R. 330, D.E.R. 331 and D.E.R. 332 epoxy resins.
• Further preferred examples are brominated bisphenol A type epoxy resins which for example have an average epoxy equivalent weight of from about 300 to about 800.
• epoxy resins can be obtained by reacting an epihalohydrin, such as epichlorohydrin with a polyhydric phenol, for example 4,4'-isopropylidene bisphenol; 2,4'-dihydroxydiphenylethylmethane; 3,3'-dihydroxydiphenyl- diethylmethane; 3,4'-dihydroxydiphenylmethylpropylmethane; 2,3'-dihydroxydiphenylethylphenylmethane; 4,4'-dihydroxy- diphenylpropylphenylmethane; 4,4'-dihydroxydiphenylbutyl- phenylmethane; 2,2'-dihydroxydiphenylditolylmethane; or 4,4'-dihydroxydiphenyltolylmethylmethane.
• an epihalohydrin such as epichlorohydrin
• a polyhydric phenol for example 4,4'-isopropylidene bisphenol; 2,
• polyhydric phenols which may be coreacted with an epihalohydrin to provide these epoxy polyethers are such .
• epoxy resins are those obtained from the reaction of polyhydric alcohols with epihalohydrins. These alcohols can be polyether polyols or polyester polyols. Preferred epoxy resins are those of the general formula: wherein,
• epoxy resins of formula II are those wherein
• R 1 , R 2 , D and q are chosen that the average epoxy equivalent weight is from 110 to 2000, most preferably from 170 to 500.
• the epoxy novolac resins can be obtained by reacting, preferably in the presence of a basic catalyst, e.g. sodium or potassium hydroxide, an epihalohydrin, such as epichlorohydrin, with the resinous condensate of an aldehyde, e.g. formaldehyde, and either a monohydric phenol, e.g. phenol itself, or a polyhydric phenol.
• a basic catalyst e.g. sodium or potassium hydroxide
• an epihalohydrin such as epichlorohydrin
• Preferred epoxy novolac resins are those of the formula wherein
• the epoxy novolac resins have preferably an average epoxy equivalent weight of from 160 to 1000, preferably from 170 to 400, most preferably from 170 to 250.
• Useful epoxy novolac resins are, e.g., those having an average value of p of 0.2, 1.7 and 2.1 which resins are commercially available from The Dow Chemical Company as D.E.N. 431, D.E.N. 438 and D.E.N. 439 resins, respectively.
• epoxy resins which are directly soluble in the polyols.
• those epoxy resins which can be brought into solution by using a solubilizing agent if necessary may also be employed.
• Solubilizing agents which chemically participate in the hardening reaction may be used. On a preferred basis, these include low viscosity monoepoxides or primary monoamines.
• the epoxy resin can be dissolved in an inert solvent, for example in a hydrocarbon like toluene, which solution can then be added to the polyol.
• epoxy hardeners can be used when preparing the polyol dispersions.
• the most useful hardeners are those compounds which have two or more -NE 2 groups.
• Suitable hydrazides include adipic acid dihydrazide and tetramethylene-1,4-carboxylic acid hydrazide.
• alkyl-substituted aliphatic, cycloaliphatic, and/or aromatic polyamines particularly di- primary amines with 1 to 4 carbon atoms in the alkyl radical and weight average molecular weights of 30 to 600, preferably 60 to 400.
• alkyl-substituted aliphatic, cycloaliphatic, and/or aromatic polyamines particularly di- primary amines with 1 to 4 carbon atoms in the alkyl radical and weight average molecular weights of 30 to 600, preferably 60 to 400.
• alkyl-substituted aliphatic, cycloaliphatic, and/or aromatic polyamines particularly di- primary amines with 1 to 4 carbon atoms in the alkyl radical and weight average molecular weights of 30 to 600, preferably 60 to 400.
• alkylene polyamines e.g.
• diamines with 2 to 12, preferably 2 to 6, most preferably 2 to 4; carbon atoms in the alkylene radical such as ethylenediamine; 1,3-diaminopropane; - 1,4-butylenediamine; 1,6-hexamethylenediamine; 1,10-deca- methylenediamine; N,N'- and N,N-dimethylethylenediamine; N-methyldipropylenetriamine; dipropylenetriamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; hexaethyleneheptamine; cycloaliphatic di- and polyamines such as 1,4-, 1,3- and 1,2-cyclohexylenediamine; 4,4'-, 2,4'- and 2,2'-diaminodicyclohexylmethane; l-methyl-2,4-diaminocyclohexane; I-methyl-2,6-diaminocyclohexane and 3-
• amine hardeners are ethanolamine; amino- ethylethanolamine; methylimino-bis(propyl)amine; imino- bis(propyl)amine; bis(aminopropyl)piperazine; aminoethylpiperazine; polyoxyalkyleneamines and bis-(p-aminocyclohexyl)methane.
• Mixtures of two or more amines are also useful.
• moles of the epoxy hardener preferably selected from the amines, are used per mole of the epoxy resins.
• epoxy hardeners which are directly soluble in the polyols.
• Epoxy hardeners which can be brought into solution by using a solubilizing agent if necessary may also be employed.
• the epoxy hardener can be solved in an inert solvent which can then be added to the polyol.
• Liquid polyols suitable as dispersing medium, have functionalities of from 2 to 8, preferably of from 2 to 4.
• “Liquid” means that the polyols are liquid at reaction temperature.
• polyester polyols and particularly polyoxyalkylene polyether polyols are preferred.
• the polyester polyols may be produced, for instance, from the reaction of polycarboxylic, preferably dicarboxylic, acids and multifunctional alcohols, preferably diols.
• the polycarboxylic acid is preferably succinic, glutaric or adipic acid.
• Preferred examples of the alcohol are ethylene glycol, 1,4-butanediol and 1,6-hexanediol.
• the polyester polyols generally have weight average molecular weights of from 200, preferably of from 800, most preferably of from 1500, to 10000, preferably to 7000, most preferably to 3500, and hydroxyl numbers of 20 to 180, preferably of 30 to 70.
• polyoxyalkylene polyether polyols which are produced by known processes such as the reaction of one or more alkylene oxides with 2 to 6, preferably 2 to 4, carbon atoms in the alkylene radical and an initiator molecule containing 2 to 8, preferably 2 to 4, active hydrogen atoms.
• Suitable alkylene oxides include 1,3-propylene oxide, 1,2- and 2,3-butylene oxide, and preferably, ethylene oxide and 1,2-propylene oxide. Tetra-. hydrofuran and styrene oxide may also be employed.
• the alkylene oxides may be used individually, alternatingly in sequence, or in mixtures.
• initiator molecules include lower polyols, polyamines and aminoalcohols having a total of two or more reactive hydrogen atoms on hydroxyl and/or primary or secondary amino groups.
• Suitable polyols include diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol and 1,6-hexamethylene glycol, triols, such as glycerol, trimethylolpropane, butanetriols, hexanetriols, trimethylolphenol, novolacs, trialkanolamines; various tetrols, such as erythritol and pentaerythritol; pentols; hexols, such as dipentaerythritol and sorbitol, and sucrose; carbohydrates; polyhydroxy fatty acid esters, such as castor oil; and polyoxyalkylated derivatives of polyfunctional compounds having three or more reactive hydrogen atom
• Higher functional aminoalcohols and polyamines include, for example, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, 2-(2-aminoethylamino) ethanol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, N-methyl- and N-ethyl-diethanolamine and triethanolamine; hydrazines; N-monoalkyl-, N,N- and N,N'-dialkyl-substituted diamines with 1 to 4 carbon atoms in the alkyl radical such as an aminoalkyl piperazine like aminoethyl piperazine; mono- and dialkyl-substituted ethylenediamines; 1,2- or 1,3-propylenediamine; 1,4-butylenediamine; 1,6-hexamethylenediamine; and 4,4'
• di- and/or trifunctional polyoxyalkylene polyether polyols having weight average molecular weights of from 200 to 10000, preferably of 800 to 7000, most preferably of 2500 to 6500, and hydroxyl numbers of 15 to 800, preferably of 20 to 200, most preferably of 25 to 60, which contain ethylene oxide as well as 1,2-propylene oxide units in the oxyalkylene chain. These units may be arranged either randomly or in blocks in the oxyalkylene chain.
• Preferred polyether polyols are those described in US Patent 3,194,773 which teaching relating to the polyols is included herein by reference.
• the most preferred polyether polyols are polyethers prepared from alkylene oxides which have 2 to 4 carbon atoms, preferably propylene oxide and/or ethylene oxide, and initiators having a functionality of two or more.
• Preferred polyethers of the branched type are those prepared by adding propylene oxide alone or in combination with ethylene oxide to various polyols, preferably diols and triols, as starters to produce adducts of various molecular weights.
• Polyethers which deserve special mention are the 1,2,6-hexanetriol, l,l,l-tris(hydroxymethyl)propane (trimethylolpropane) and glycerol adducts of propylene oxide or propylene oxide/ethylene oxide having molecular weights (weight average value) of from 1000 to 10 000, preferably from 2000 to 7000.
• These polyethers can be homo-or heteropolymers.
• polyethers are block copolymers prepared from propylene and ethylene oxide with the above described higher functional initiators. Block copolymers containing no more than about 35 weight percent of ethylene oxide are- preferred.
• the most preferred polyether polyols are those derived from glycerol as an initiator which is first partially alkoxylated with a C 3-4 alkylene oxide component, for example 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, preferably 1,2-propylene oxide, and the intermediate then is ethoxylated with ethylene oxide. These polyols are, for example, represented by the following formula IV wherein
• polyether polyols which are derived from glycerol as an initiator and which is alkoxylated with 1,2-propylene oxide and ethylene oxide to give a polyol with randomly distributed propylene oxide and ethylene oxide groups.
• the epoxy resin and the epoxy hardener can be reacted in one of the above mentioned polyols.
• the epoxy hardener and the - epoxy resin can be reacted in an organic inert solvent like a benzene, toluene or tetrahydrofuran, and then added to the polyol.
• catalysts are known in the art. Suitable catalysts are; for example, amines, preferably ethylene diamine, diethylene triamine, triethylene tetraamine, aminoethyl piperazine, organic acids, e.g. dicarboxylic acids, phenol compounds, imidazole and its derivatives, and calcium nitrate. Imidazole is a preferred catalyst.
• the produced polymer polyol dispersions contain 1 to 50 percent by weight of polymer particles, preferably 5 to 30 percent by weight, based on the total dispersion weight. With a polymer content of 10 percent by weight in the polyether polyol at 25° C, the dispersions generally have viscosities of up to 2500 mPa ⁇ s, preferably from 1000 to 1700 mPa ⁇ s.
• the polymer particles in the dispersion generally have average diameters of 10 nm to 10000 nm, preferably of 50 nm to 5000 nm, most preferably of 100 nm to 3000 nm.
• the polymer polyol dispersions are reacted with polyisocyanates in the presence of a blowing agent.
• the polyol dispersion Before reacting the polyol dispersion with the polyisocyanate(s), the polyol dispersion can be mixed with any unmodified - polyol, as mentioned above.
• the polyol used as dispersing agent in the dispersion and the polyol used for diluting the disperson can be the same.
• any organic polyisocyanate may be used.
• useful isocyanates include, for example, ethylene diisocyanate; 1,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-iso- cyanato-3,3,5-trimethyl-5-isocyanato-methylcylohexane (German Auslegeschrift 12 02 785); 2,4- and 2,6-hexahydro- toluylene diisocyanate as well as any mixtures of these isomers; hexahydro-1,3- and/or -1,4-phenylenediisocyanate; perhydro-2,4'- and/or -4,4'-diphenylmethanediisocyanate; 1,3- and 1,4-phenyl
• Useful polyisocyanates are furthermore those described in US Patent 3,194,773. It is also possible to use the distillation residues containing isocyanate groups which accumulate in the industrial-scale production of isocyanates, optionally in solution in one or more of the above mentioned polyisocyanates. It is also possible to use mixtures of the aforementioned polyisocyanates.
• polyisocyanates such as 2,4- and 2,6-toluene diisocyanate or mixtures of these isomers (TDI), polyphenyl-polymethylene polyisocyanates, of the type obtained by condensing aniline with formaldehyde, followed by phosgenation (crude MDI); or polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (so-called modified polyisocyanates) or mixtures of any of these polyisocyanates.
• TDI 2,4- and 2,6-toluene diisocyanate or mixtures of these isomers
• CADI phosgenation
• polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups so-called modified polyisocyanates
• the organic polyisocyanate is employed in an excess of 0 to 25 weight %, preferably 0 to 15 weight %, based on the weight of polyisocyanate consumed in the reaction.
• blowing agents employed in the process of this invention include any compound capable of generating an inert gas under the conditions used to produce the foaming reaction product (e.g. by reaction to produce a gas or by volatilization).
• Suitable blowing agents include volatile halocarbons (especially chlorocarbons and chlorofluor- carbons) such as trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, bromotrifluoromethane, chlorodifluoromethane, chloromethane, 1,1-di- chloro-1,1-fluoroethane, 1,1-dichloro-1-fluoroethane, 1-chloro-ethane, 1,1-difluoroethane, 1,1-dichloroethane, 1,2,2-trichloroethane, chloropentafluorethane, 1-chloro-1-fluore
• blowing agents include low-boiling hydrocarbons such as butane, pentane, hexane, cyclohexane and the like. Mixtures of blowing agents can be used as well. Furthermore, gas generating blowing agents, for example water, are suitably used.
• blowing agents are, for example, described in US patents 4,125,487 and 3,753,933 and so much of these patents as pertains to blowing agents is incorporated . herein by reference.
• Foaming can also be caused by injecting an inert gas into the reaction mixture.
• Suitable inert gases include, for example, nitrogen, oxygen, carbon dioxide, xenon, helium and mixtures thereof such as air.
• blowing agent employed will vary with the density desired in the foam product and the blowing agent used.
• Volatile halocarbons or hydrocarbons can generally be used in an amount of from 1 to 50, preferably of from 2 to 30, weight percent, based on the weight of the polyol of the polymer polyol dispersion.
• Water can generally be used in an amount of from 0 to 6, preferably of from 0.5 to 5, most preferably of from 1.5 to 4 weight percent, based on the weight of polyol of the polymer polyol dispersion.
• foaming catalysts for example foaming catalysts, silicones, coloring agents and fire retardant agents may be used when producing the foams.
• Suitable organo-metal catalysts include, for example, organo-metal compounds or salts of tin, for example those described in US patent 3,194,773, zinc, lead, mercury, cadmium, bismuth, antimony, iron, manganese, cobalt, copper or vanadium.
• Suitable amine catalysts include, for example, triethylenediamine, triethylamine, tetramethylbutanediamine, N,N-dimethylethanolamine, N-ethylmorpholine, bis-(2-dimethylaminoethyl)ether, N-methylmorpholine N-ethylpiperidine, 1,3-bis-(dimethylamino)-2-propanol, N,N,N',N'-tetramethylethylenediamine, or mixtures thereof.
• Suitable alkali metal alkoxides which can be employed include, for example, sodium ethoxide, potassium ethoxide, sodium propoxide, potassium propoxide, sodium butoxide, potassium butoxide, potassium propoxide, sodium butoxide, potassium butoxide, lithium ethoxide, lithium propoxide, lithium butoxide, alkali metal salts of polyols such as described in U.S. Patent 3,728,308, or mixtures thereof.
• these urethane catalysts are in liquid form, but if they are inherently a solid at the application temperature, then they may be dissolved in an appropriate liquid, such as, for example, dipropylene glycol or they may be dissolved or dispersed in one of the components.
• an appropriate liquid such as, for example, dipropylene glycol or they may be dissolved or dispersed in one of the components.
• the catalysts when employed, can be employed in quantities of from 0.001 to 5, preferably from 0.01 to 2 parts per 100 parts of total polyol employed depending on the activity of the catalyst. Very weak catalysts could be employed in quantities above 5 parts per 100 parts of polyol. The parts are weight parts.
• cell control agents can be employed. Suitable cell control agents which can be employed herein include silicone oils such as, for example, DC-193, DC-195, DC-197 and DC-198 commercially available from Dow Corning Corp.; SF-1034, PFA-1635, PFA-1700 and PFA-1660 commercially available from General Electric Co.; L-520, L-5320 and L-5340 commercially available from Union Carbide Corp.; and B-1048 and B-4113, B-4380, B-8629 and B-8650 commercially available from TH. Goldschmidt, AG., or mixtures thereof. Cell control agents, when employed, can generally be employed in quantities of from 0.1 to 5.0, preferably of from 0.2 to 2.5 weight %, based upon the total weight of polyols used.
• silicone oils such as, for example, DC-193, DC-195, DC-197 and DC-198 commercially available from Dow Corning Corp.; SF-1034, PFA-1635, PFA-1700 and PFA-1660 commercially available from General Electric Co.; L-520,
• the process of the present invention differs from the known processes in that above mentioned polymer polyol dispersions are employed alone or in combination with conventional unmodified polyols for reacting with polyurethanes.
• the properties of the foams produced therefrom can be improved in the desired manner.
• the hardness, the tensile strength and the tear strength can be increased considerably, compared to foams which have been prepared using unmodified polyols.
• polyether triol (1) 93.8 g polyether triol (1) are charged into a 100 ml glass flask and 20.0 g epoxy resin (2) are added to the polyol (1). The mixture is stirred with a magnetic stirrer until a clear solution results. 3.45 g ethylene diamine is then added (the molar ratio between the ethylene diamine and the epoxy resin (2) being 1.0). The resulting mixture is stirred for about three minutes. The flask is then transferred into an oven of 50° C wherein the polymer polyol dispersion builds in 48 hours. The calculated solids content of the dispersion is 20%.
• Example Al is repeated by utilizing 91 g polyether triol (1), 20 g epoxy resin (2) and 2.76 g ethylene diamine. The calculated solids content of the dispersion is again 20%.
• the mixture is left at room temperature for 24 hours and afterwards transferred into an oven at 60°C wherein the polymer polyol dispersion builds in 48 hours.
• the calculated solids content of the dispersion is 15.7%.
• the solids content is calculated as the sum of the weight of the epoxy resin (2) and the the ethylene diamine divided by the weight of the total reaction mixture.
• the isocyanate index is from 90 - 110.
• the isocyanate index minus 100 indicates the molar excess of isocyanate over the stoichiometric amount required for the reaction with the polyol and water (in percent).
• the physical properties of the foams are measured according to the following standard methods:
• a mixture of 60 weight parts polyether triol (1) and 40 weight parts polymer polyol dispersion Al is prepared.
• the mixture has a weight of about 2 kg.
• the following compounds are added to the mixture: The mixture is stirred for 60 sec. at 1400 revolutions per minute using a 90 mm mixing disc. The temperature of the mixture is adjusted to 20°C ⁇ 0.5°C.
• the isocyanate mixture (4) also at 20°C ⁇ 0.5°C is added quickly to the above mentioned mixture and stirred for 8 sec. before it is poured into a test mould of 56 cm x 59.5 cm x 15 cm. The temperature of the mould is maintained at 30°C, and the resulting foam piece is removed from the mould after 10 minutes.
• a mixture of 50 weight parts polyether triol (1) and 50 weight parts polymer polyol dispersion A2 is prepared.
• the mixture has a weight of about 2 kg.
• the additional components and the conditions for producing the foam are the same as in examples 1 to 6.
• the isocyanates and all other additives used are the same as used in examples 1 to 6.
• the foam pieces are produced as described in examples 1 to 6.
• Examples 1 to 7 and comparative examples A to E show that a considerably increased tear resistance, tensile strength and hardness (40 % compression load deflection, CLD) is attained when a polymer polyol dispersion described herein is used for producing the polyurethane foams of the present invention.
• a mixture of 40 weight parts polyether triol (1) and 60 weight parts polymer polyol dispersion A3 is prepared.
• the mixture has a weight of about 2 kg.
• the mixture is stirred for 60 sec. at 1400 revolutions per minute using a 90 mm mixing disc.
• the temperature of the mixture is adjusted to 20°C ⁇ 1°C.
• the isocyanate mixture (4) at 20°C ⁇ 1°C is quickly added to the polyol and stirred for 8 sec. before it is poured into a test mould of 56 cm x 59.5 cm x 15 cm. The temperature of the mould is held at 30°C and the resulting foam piece is removed from the mould after 10 minutes.
• Examples 8 to 10 and comparative examples F to H demonstrate again that considerably increased tear resistance, . tensile strength and hardness (40% CLD) is attained when a polymer polyol dispersion described herein is used for producing the polyurethane foams of the present invention.
• the solids content of the resulting dispersion is 30 percent.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=10592329

Family Applications (1)

Country Status (5)

Cited By (3)

Families Citing this family (28)

Citations (4)

Family Cites Families (3)

• 1986
  • 1986-01-31 GB GB868602446A patent/GB8602446D0/en active Pending
• 1987
  • 1987-01-28 EP EP87300752A patent/EP0232124A3/fr not_active Withdrawn
  • 1987-01-30 US US07/031,350 patent/US4789690A/en not_active Expired - Fee Related
  • 1987-01-30 JP JP62018756A patent/JPS62215620A/ja active Pending
  • 1987-01-30 CA CA000528531A patent/CA1272848A/fr not_active Expired - Fee Related

Patent Citations (4)

Also Published As

Similar Documents

Legal Events